Photographic light-sensitive material

ABSTRACT

THIS INVENTION RELATES TO A PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL COMPRISING A HIGHLY-REFLECTIVE SUPPORT WITH A LUSTROUS SURFACE COATED WITH AT LEAST ONE LAYER OF MICROCAPSULES CONTAINING A SILVER HALIDE EMULSION.

Oct. 3l, 1972 ASAJI KoNDo ErAL 3,701,663

PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL Filed Oct. 5. 1969 FIG. I

FIG. 3

IOR |06 FIG. 5

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INVENTORS ASAJI KONDO HIROSHI FUJISAKI` SHIZUO MIYANO KENICHIRO YAZAWASLLW, WI

ATTORNEYS United States Al-"atent Oice .'i,70l,ti63l Patented Oct. 3 1,1972 3,701,663 PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL Asaji Kondo,Hiroshi Fujisaki, Shzuo Miyano, and Kenichiro Yazawa, Asaka-sh, Japan,assignors to Fuji Photo Film Co., Ltd., Kanagawa, Japan Filed Oct. 3,1969, Ser. No. 863,645 f Claims priority, application Japan, Oct. 4,1968, 43/ 72,273 Int. Cl. G03c 1/94 U.S. Cl. 96-86 16 Claims ABSTRACT oFTHE DISCLOSURE This invention relates to a photographic light-sensitivematerial comprising a highly rellective support with a lustrous surfacecoated with at least one layer of microcapsules containing a silverhalide emulsion.

. DESCRIPTION OF THE INVENTION 1 .This invention relates to aphotographic light-sensitive material for use as a print and, moreparticularly, it is concerned with a photographic light-sensitivematerial for use as a print in which a microcapsule-type emulsion usedin black-and-white or color photography is coated onto a support whichreilects light well and has a metallic luster.

The microcapsule-type emulsion described in the invention is intended tocover a particulate emulsion in which photographic elements, such assilver halide, coupler and additives, are coated with a gelatincoacervate, as disclosed in Japanese Pat. 496,245, a particulateemulsion in which a gelatin silver halide emulsion is coated with ahydrophobic polymer iilm, as disclosed in British Pat. 864,060, or apacket emulsion as disclosed in U.S. Pat. 2,698,794.

The present invention will now be illustrated by reference to theaccompanying drawings, in which the photographic light-sensitivematerial of this invention is compared with a well-known photographiclight-sensitive material for use as a print.

FIG. 1 and FIG. 2 are cross-sectional views of the known photographiclight-sensitive material used in blackand-white and color printing,respectively;

FIG. 3 and FIG. 4 are cross-sectional views of the microcapsule-typeemulsions used in black-and-white photography and color photography,respectively; and

' FIG. 5 and FIG. 6 are cross-sectional views of the photographiclight-sensitive materials used in this invention in black-and-white andcolor printing, respectively.

The commonly used photographic light-sensitive materials for printingcomprise a lilm or a paper having a ,white pigment layer, for instance,baryta paper, and one vormore emulsion layers coated on the paper. FIG.1

shows a cross-sectional view of the commonly used photographiclight-sensitive material used in black-and-white printing, in which thelight-sensitive emulsion layer 6, consisting of gelatin 4 and silverhalide S, is coated onto support consisting of paper 1 and baryta layer2. Referring to FIG. 2, the blue-sensitive emulsion layer 6B,

the green-sensitive emulsion layer 6G and the red-sensio'f amicrocapsule-type emulsion 10 for color printing used in this inventionwherein silver halide S and coupler 7 are coated with gelatin coacervate8. The type of silver halide and coupler diifer depending on whether theemulsionv is to be used as the blue-sensitive layer, the greensensitivelayer or the red-sensitive layer, of course. FIG. 5 shows across-sectional View of the photographic lightsensitive material forblack-and-white printing used in this invention in which ablack-and-white microcapsule type emulsion 9 is coated on a metalliclustrous surface of an aluminum plate 12 with a binder 11. FIG. 6` showsa cross-sectional view of the photographic light-sensitive material forcolor printing used in this invention in which a blue-sensitivemicrocapsule-type emulsion 10B, a greensensitive microcapsule-typeemulsion 10G, and a red-sensitive microcapsule-type emulsion 10K arecoated onto an aluminum plate 12 having a subbing layer 13 on itsmetallic lustrous surface.

According to this invention, when a microencapsulated black-and-whiteemulsion or color emulsion is applied to a lustrous surface of analuminum plate, the image, obtained on exposing and developing, isunexpectedly bright. Furthermore, this image has the appearance of atransparent positive and the feeling of printing'paper. This effect isremarkably evident, specifically in this color areas or highly lightedareas, giving the image a number of bright points in the depth of auniform color as if a metal powder coated surface or metallic coatingwere being viewed.

While not desiring to be bound by theory the following reasons may giverise to this phenomenon:

1) The aluminum surface used as the support reflects light well;

(2) The particles on the surface of the aluminum plate consist mainly ofgelatin and light passes through it well and is scattered;

(3) With a color image, in the red area, the green-sensitive capsulesand blue-sensitive capsules form colors, such as magenta and yellow,respectively, forming the red image. The red-sensitive microcapsules,which are unexposed and thus uncolored, exist as transparent particles.Light passing through these particles causes the bright points. Y p.

Although the image obtained on a photographic lightsensitive material inwhich the usual emulsion is applied to an aluminum plate is generallybrighter than the image obtained when the same photographiclight-sensitive materials are applied to a baryta paper, theabove-mentioned phenomenon is not observed.

'I'he photographic material of the invention has another advantage inthat the surface is naturally matted because the microcapsules areexposed as particles. As a result, the visual stimulus is different thanthat obtained with prior art images. Moreover, the microcapsule-typeemulsion used in making a photographic light-sensitive material forcolor printing, by mixing the three color capsules, can be coated all atonce. Accordingly, a thick metal plate can readily be coated as asupport, as well as aluminum foil and iilms of vacuum-depositedaluminum.

Commonly used photographic elements can be incorporated into themicrocapsule, e.g., oils, dyes and additives, in addition to the silverhalides, couplers and protective colloids normally used.

The microcapsule-type emulsion used in the invention can be preparedaccording to the method disclosed in Japanese Pat.r 496,245.

As the support to which the microcapsule-type emulsion is applied, asupport having a metallic luster or high reflectance factor for light isdesirable. As the uniformly smooth surface, a surface of metals andalloys, such as aluminum plates and foils, laminates, such asaluminumpolyethylene-paper or aluminum-vinyl chloride-paper, and

metals, such as stainless steel, chromium and nickel and alloys thereofcan be used. In addition, a polyester iilm on which a metal has beenvacuum-deposited, for example, Metalmie (manufactured by Toyo 'RayonCo., Ltd.) can be used. Where a black-and-white image is to be obtained,a pink, green or gold support gives a photographic image having thecolor characteristics of the support. In addition, some aluminum oralloy sheets are manufactured with narrow lines in one direction duringrolling and can Ibe used as the support having anisotropy. The supportcan previously be subbed to protect the surface as well as to improvethe adhesion of adhesives.

The following examples are given to illustrate the invention in detailwithout limiting the scope thereof.

EXAMPLE 1 Photographic light-sensitive material containing amicrocapsule type emulsion for black-and-white photography In thepresence of a photographically safe light, a gelatino silver iodobromideemulsion (100 g.) containing 4% silver halide (based on silver nitrate)and 12% gelatin was added to a solution of 30 ml. of a 4%naphthalenesulfonic acid-formalin condensate in 840 m1. of water, heldat 40 C. and then mixed with agitation with 39` ml. of a 1% aqueoussolution of acetic acid to lower the pH to 4.5. A complex coacervate ofgelatin and the foregoing condensate surrounded the silver halidecrystal forming a spherical microcapsule of about 5 microns. Thisproduct was then poured into a second vessel containing 3 liters of icewater and 0.6 g. of chrome alum, and the pH was raised to 6 by addingsodium carbonate. After stirring the mixture for l hour, the mixture wasallowed to stand at room temperature. The following day, the supernatantliquid was removed and a hardened c psule slurry was obtained bycentrifugal separation. 100 g. of 110% gelatin was added to the slurryas a binder to obtain a black and white microcapsule-type emulsion.

The black-and-white microcapsule-type emulsion'prepared as above wasapplied to an aluminum sheet, 210 microns thick and having a mirrorsurface at a level of 500 g./m.2. The material was allowed to set andthen dried.

When the coated light-sensitive aluminum sheet is exposed to light usinga black and white negative, and subsequently developed, a print havingunexpectedly bright image is obtained.

EXAMPLE 2 Photographic light-sensitive material containing amicrocapsule-type emulsion for color photography Microcapsulesconventionally used in color photography, i.e., microcapsules containinga blue-sensitive silver halide and a yellow coupler, microcapsulescontaining a green-sensitive silver halide and a magenta coupler andmicrocapsules containing a red-sensitive silver halide and a cyancoupler, were prepared according to the method described in Japanesepatent publication No. 12948/ 1965. The size of the microcapsulesprepared ranged from 15 to 30 microns, 25 g. of each of theymicrocapsule slurry were mixed, the slurry added to 60 g. of 20% gelatinand then the mixture was diluted with water to 7010 ml.l 1 30 ml. of theresulting mixture was coated onto an aluminum sheet having a mirrorsurface and allowed to set and be dried. The mirror surface aluminumsheet had previously been undercoated with a polyester resin and thenwith gelatin. The film thickness of the dried microcapsule emulsion wasapproximately 35 microns The resulting photographic material was exposedto light through a color negative and then subjected to development. Acolor image of unexpected brightness was obtained.

What is claimed is: l

'.l. In a conventional photographic light-sensitive material for use informing a positive black-and-white or 4 color image, which consistsessentially of a support material having coated thereon, a silver halidephotographic emulsion, the improvement which comprises:

employing a support material which exhibits a high reillectance factorfor light and further exhibits a metallic lustrous surface and employingsaid silver halide emulsion in the form of at least one layer ofmicrocapsules.

2. The photographic light-sensitive material of claim 1, wherein saidsupport is an aluminum foil vacuum deposited on polyethyleneterephthalate film. y

3. The photographic light-sensitive material of claim 1, wherein saidsupport has a subbing layer.

4. The photographic light-sensitive material of claim 1,', wherein saidmicropsule contains a color coupler capable of forming a color dye imageby reaction of an oxidation product of a developer.

5. The photographic light-sensitive material of claim 1, wherein saidmicrocapsules are produced by a coacervation of gelatin.

6. The photographic light-sensitive material of claim 11, wherein saidsupport is a metal selected from the group consisting of aluminum,stainless steel, chromium, nickel, and alloys thereof.

7. 'Ihe photographic light-sensitive material of claim 6, wherein saidaluminum represents a member selected from the group consisting ofaluminum plate and aluminum foil.

8. The photographic light-sensitive material of claim 7, wherein thesurface of said aluminum contains elongated irregularities.

9. The photographic light-sensitive material of claim 7, wherein thesurface of said aluminum is a rellecting mirror surface.

10. The photographe light-sensitive material of claim 9, wherein themirror surface is at a level of 500 g./m.'2.

11. The photographic light-sensitive materiall of claim 7, wherein thethickness of said aluminum plate and foil is 210 microns.

12. The photographic light-sensitive material of claim 1, wherein saidsupport is a laminate.

13. The photographic light-sensitive material of claim 12, wherein thelaminateis a laminate of aluminum foil on a vinyl chloride-coated paper.

14. The photographic light-sensitive material of claim 12, wherein thelaminate is a laminate of aluminum foil on a polyethylene-coated paper.

15. The photographic light-sensitive material of claim 14, wherein thesurface of said aluminum contains elongated irregularities.

16. The photographic light-sensitive material of claim 14, wherein thesurface of said aluminum is a reflecting mirror surface. ReferencesCited UNITED STATES PATENTS 2,215,128 9/1940 Meulendyke 96-86 X`2,257,143 9/1941 Wood 96-86 X 2,637,929 5/ 1953 Hausman 96-86 UX3,342,601 9/'1967 Houle et al 96-86 3,365,350 1/ 1968 Cahn 161--63,551,150 12./ 1970 Woodward et al 96-86 X 2,698,794 1/ 1955 Godowsky96-97 3,061,435 10/1962l Tomanek et al 96-86 X 3,161,518 12/ 1964 Dealet al 96-86 X e FOREIGN PATENTS 864,060 3/1961I Great Britain.

ROBERT F.. BURNETT, Primary Examiner I.. C. GIL, Assistant Examiner U.S.Cl. X.R. 96-96; 99

